JP5212418B2 - Resin production method - Google Patents

Description

  The present invention relates to a novel carboxyl group-containing amide imide resin, a carboxyl group-containing imide resin, a production method thereof, and a thermosetting resin composition containing them. The thermosetting resin composition is useful for various heat-resistant coating materials and electrical insulating materials such as interlayer insulating materials for printed wiring boards, build-up materials, semiconductor insulating materials, and other heat-resistant adhesives. A functional imide resin composition is provided.

  In recent years, improvement in heat resistance and electrical characteristics has been demanded in various fields mainly in the electrical and electronic industry. Under such circumstances, various heat-resistant materials have been developed. In particular, aromatic polyimide is an important material in terms of its excellent heat resistance and mechanical properties. In general, a polyimide resin is prepared by synthesizing an amic acid in a polar solvent from a polyvalent carboxylic acid anhydride and a diamine. Is to do. This uses a polyamic acid intermediate solution because the imide resin does not dissolve in the solvent. In addition, when creating a polyimide resin-based coating film on a specific substrate or the like, a method of coating such a polyamic acid solution is taken, but when imidizing from a polyamic acid, the treatment is performed at a very high temperature. There is a limit to the substrates that can be used due to the need to perform dehydration and imide ring closure. Since polyamic acid compounds are also highly polar, they are soluble only in polar solvents such as dimethylacetamide (DMA), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), methylpyrrolidone (NMP), and γ-butyrolactone. There is a problem from the viewpoint of environmental and environmental conservation. In addition, polyamic acid is a material that is very easily hydrolyzed, and has a drawback that it tends to cause stability problems due to water absorption of the solvent during synthesis or storage. Such polar solvents containing nitrogen and sulfur, γ-butyrolactone, and the like are excellent in solubility, but are also very hygroscopic solvents and are very difficult to handle as polyamic acid solutions.

  Further, a composition having a polyamideimide resin as a main component as a heat resistant resin has been proposed. Specifically, JP-A-55-137161, JP-A-56-8453, JP-A-57-165450, JP-A-57-167345, JP-A-58-174441, etc. contain an isocyanurate ring. A polyamidoimide resin for synthesizing a polycarboxylic acid containing a polyisocyanate, an aromatic isocyanate, a lactam and an acid anhydride in a cresol solvent is disclosed. These technologies provide materials dissolved in cresol solutions, but when forming a coating film, the use of odor-resistant, toxic materials such as cresol deteriorates the working environment and is also environmentally friendly. It gives a load. Furthermore, a lactam or cresol solvent causes a reaction with an isocyanate group and becomes a blocking agent. Therefore, it not only acts as an inhibitor of molecular growth during the reaction, but also has the disadvantage that good physical properties cannot be obtained by reacting with other curing components (for example, epoxy resins) during thermal curing. Furthermore, if the blocking agent is removed, it has the disadvantage of causing contamination of the equipment used and other materials.

  JP-A-59-204613, JP-A-59-142225 and the like disclose compositions such as particulate polyamideimide resin and epoxy resin obtained by non-aqueous dispersion polymerization. These are technologies that improve the solubility of imide resins by fundamentally using particulate materials. However, since they are particulate, there are problems with their coatability, uniformity, and leveling with the substrate. This includes problems such as painting methods and voids. Further, since a surfactant is used to maintain the particulate form during production, it involves many problems such as heat resistance after curing and generation of thermal decomposition products.

  That is, imide-based resins having high heat resistance cannot be dissolved in ordinary general-purpose solvents with the currently disclosed technology, and when various modifications and methods are adopted to improve solvent solubility, At present, physical properties, environmental performance, and properties are sacrificed.

JP-A-55-137161 JP-A-56-8453 JP 57-165450 A JP-A-57-167345 JP 58-174441 A JP 59-204613 A JP 59-142225 A

  Accordingly, the present invention provides a novel thermosetting resin composition that improves the heat resistance and electrical properties of the thermosetting resin, is soluble in a solvent, and has excellent paintability, workability, and working environment, and the composition It is an object of the present invention to provide a novel resin constituting a product and a method for producing the resin.

  As a result of intensive studies to solve the above problems, the present inventor has found that an aliphatic isocyanate compound and / or an alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule, and a tricarboxylic acid anhydride (b1 ) And / or tetracarboxylic anhydride (b2) and a novel carboxyl group-containing amideimide resin, carboxyl group-containing imide resin, and an epoxy compound having two or more epoxy groups in the molecule The curable amide imide resin composition and the curable imide resin composition are improved in heat resistance and electrical characteristics, soluble in solvents, and excellent in paintability, workability, and work environment. The headline and the present invention were completed.

  That is, the present invention relates to an aliphatic isocyanate compound and / or an alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule, a tricarboxylic acid anhydride (b1) and / or a tetracarboxylic acid anhydride ( b2) is a method for producing a carboxyl group or an acid anhydride group-containing amideimide resin or a carboxyl group or an acid anhydride group-containing imide resin by reacting with b2) in a polar solvent not containing a nitrogen atom and a sulfur atom. The polar solvent is an ether solvent, and the aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule contains an isocyanurate type polyisocyanate (a2). A resin production method characterized by the above is provided. The present invention also provides a method for producing a resin in which the carboxyl group or acid anhydride group-containing amideimide resin, the carboxyl group or acid anhydride group-containing imide resin has an acid value of 60 to 200 KOHmg / g. In the present invention, the aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule is composed of a diisocyanate monomer (a1) and an isocyanurate type polyisocyanate (a2). Or composed only of the isocyanurate type polyisocyanate (a2), and the weight ratio ((a1) / (a2)) of the diisocyanate monomer (a1) and the isocyanurate type polyisocyanate (a2) is from 0 to The present invention provides a method for producing a resin characterized by being 0.5.

  The curable amide imide resin composition and curable imide resin composition of the present invention have excellent solubility in general general-purpose solvents while having an imide bond in the resin structure, and have excellent workability, coating suitability, and heat resistance. It has excellent performance in cured properties such as durability and electrical properties, and other durability. Moreover, the carboxyl group-containing amideimide resin and / or carboxyl group-containing imide resin of the present invention are useful for the production of such a curable amideimide resin composition and / or curable imide resin composition.

  In the carboxyl group-containing amideimide resin and / or amideimide resin of the present invention, the aliphatic isocyanate compound having two or more isocyanate groups in the molecule and the alicyclic socyanate compound (a) improve solubility in a general-purpose solvent. It is an essential material and is preferably 70% by weight or more of the total isocyanate raw material. In consideration of crystallization over time during the reaction, it is particularly preferably 80% by weight or more of the total isocyanate raw material.

  Examples of the aliphatic isocyanate compound and alicyclic isocyanate compound include, as a bifunctional isocyanate monomer (a1), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-dicyclohexylmethane diisocyanate, and hydrogenated xylene diisocyanate. Aliphatic and alicyclic isocyanates such as (HXDI), norbornylene diisocyanate (NBDI), and lysine diisocyanate. Further, isocyanurates of polyisocyanates such as nurate (polyisocyanate, (a2)) such as IPDI3N (isophorone diisocyanate isocyanurate type triisocyanate), HDI3N (hexamethylene diisocyanate isocyanurate type triisocyanate), HXDI3N ( Hydrogenated xylene diisocyanate isocyanurate type triisocyanate), NBDI3N (norbornane diisocyanate isocyanurate type triisocyanate), and the like. Furthermore, the buret body of the said isocyanate compound and the adduct body obtained by the urethanation reaction of the said isocyanate compound and various polyols can also be used. In particular, in terms of heat resistance, thermal properties such as TG, and solvent solubility, the combined use of the bifunctional isocyanate monomer (a1) and the isocyanurate type polyisocyanate (a2) or the sole use of the isocyanurate type polyisocyanate (a2) preferable.

  Aromatic isocyanates (a3) can be used in combination as long as the non-crystallinity of the system is not impaired, but the amount is preferably 30% or less, particularly preferably 20% or less, based on the total isocyanate compound. That is, W-NC0 (total isocyanate compound (weight)) = W (a1) + W (a2) + W (a3), where W (a1), W (a2), and W (a3) are (a1), ( The weight of each of a2) and (a3) and the use range (weight ratio) of the aromatic isocyanate is preferably W (a3) / {W (al) + W (a2) + W (a3)} ≦ 0.3. Yes, and particularly preferably W (a3) / {W (a1) + W (a2) + W (a3)} ≦ 0.2. Representative examples of such aromatic isocyanates include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4, 4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4'-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, naphthalene diisocyanate, etc. It is done. Similarly, polyisocyanate raw materials such as one or more burettes or nurates of such isocyanate monomers can be used, and adducts obtained by urethanization reaction of the isocyanate compound and various polyols can also be used.

  In the present invention, by directly forming an imide bond from the above-mentioned isocyanate compound and a specific acid anhydride, a resin having good reproducibility and good solubility without passing through a polyamic acid intermediate having a problem in stability or the like. The system can be synthesized.

  The tricarboxylic acid anhydride (b1) and / or tetracarboxylic acid anhydride (b2) used in the present invention is preferably an aromatic acid anhydride compound. Specifically, tricarboxylic acid anhydrides such as trimellitic anhydride and naphthalene-1,2,4-tricarboxylic acid anhydride; pyromellitic dianhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic acid Acid dianhydride, diphenyl ether-3,3 ', 4,4'-tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3'4,4 '-Tetracarboxylic dianhydride, biphenyl-2,2'3,3'-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2, 4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8 -Dimethyl-1, , 3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, fetentene -1,3,9,10-tetracarboxylic dianhydride, berylene-3,4,9,10-tetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis ( 3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride , 2,2-bis (2,3 Dicarboxyphenyl) propane dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-di Carboxyphenyl) ether dianhydrides and the like include tetracarboxylic acid anhydrides having an aromatic organic group in the molecule, and these can be used alone or in combination. Further, a tricarboxylic acid anhydride and a tetracarboxylic acid anhydride may be mixed and used. In some cases, bifunctional dicarboxylic acid compounds such as adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid and acid anhydrides thereof may be used in combination.

  Reacting an aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule with a tricarboxylic acid anhydride (b1) and / or a tetracarboxylic acid anhydride (b2); And when obtaining the carboxyl group-containing amide imide resin and / or carboxyl group-containing imide resin of this invention, it is preferable to make it react in the polar solvent which does not contain a nitrogen atom and a sulfur atom. In the presence of a polar solvent containing nitrogen and sulfur atoms, environmental problems are likely to occur, and in the reaction of such an isocyanate compound with tricarboxylic anhydride (b1) and / or tetracarboxylic anhydride (b2). And molecular growth is likely to be hindered. When such a molecule is cut, the physical properties of the composition are likely to deteriorate, and film defects such as “repellency” tend to occur.

  In the present invention, the polar solvent containing no nitrogen atom and sulfur atom is more preferably an aprotic solvent. For example, a cresol solvent is a phenolic solvent having protons, but is somewhat unfavorable in terms of the environment, and easily reacts with an isocyanate compound to hinder molecular growth. In addition, the cresol solvent easily reacts with an isocyanate group to easily become a blocking agent. Therefore, it is difficult to obtain good physical properties by reacting with other curing components (for example, epoxy resin) during thermal curing. Furthermore, if the blocking agent is removed, it is likely to cause contamination of the equipment used and other materials. Also, alcohol solvents are not preferred because they react with isocyanates or acid anhydrides. Examples of the aprotic solvent include ether-based, ester-based, and ketone-based solvents having no hydroxyl group, and among these, ether-based solvents having no hydroxyl group are particularly preferable.

  In the present invention, the polar solvent containing no nitrogen atom and sulfur atom is more preferably an ether solvent. The ether solvent has a weak polarity and has an aliphatic isocyanate compound and / or an alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule, a tricarboxylic acid anhydride (b1) and / or Alternatively, it provides an excellent reaction field in the reaction with the tetracarboxylic acid anhydride (b2). As such ether solvents, known and commonly used solvents can be used. For example, ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Polyethylene glycol dialkyl ethers such as triethylene glycol dimethyl ether, triethylene glycol diethyl ether and triethylene glycol dibutyl ether; ethylene glycol monomers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate Alkyl ether acetates; polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether Polypropylene glycol dialkyl ethers such as tellurium, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol dibutyl ether; propylene glycol monoalkyl such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate Ether acetates: Dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene group Polypropylene glycol monoalkyl ether acetates such as recall monobutyl ether acetate; or dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymers; monoacetate monoalkyl ethers of copolymerized polyether glycols; or Such polyether glycol alkyl esters; polyether glycol monoalkyl esters monoalkyl ethers, and the like.

  The aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule is reacted with the tricarboxylic acid anhydride (b1) and / or the tetracarboxylic acid anhydride (b2). In this case, the number of moles (N) of the isocyanate group of the aliphatic isocyanate compound and / or the alicyclic isocyanate compound (a) and the carboxyl group of the tricarboxylic acid anhydride (b1) and / or the tetracarboxylic acid anhydride (b2). The number of moles (M1) and the number of moles of acid anhydride groups (M2) preferably satisfy the following formula. 3> ((M1) + (M2)) / (N))> 1.1. Particularly preferably, 2> ((M1) + (M2)) / (N))> 1.2. At this time, if the sum of the number of moles of carboxyl groups (M1) and the number of moles of acid anhydride groups (M2) is larger than the number of moles of isocyanate groups (N), the polarity in the reaction system increases. The reaction proceeds to lubrication. When the above ratio is deviated, for example, 1.1 or less, the isocyanate group remains and the stability and the like tend to be slightly deteriorated. In the case of 3 or more, the acid anhydride-containing compound remains and tends to be in a state of separation such as recrystallization.

  The blending ratio ((b2) / (b1)) of the tetracarboxylic anhydride (b2) and the tricarboxylic anhydride (b1) is preferably a ratio of 0-2. When the blending ratio of the tetracarboxylic acid anhydride (b2) exceeds this range, the concentration of the imide bond increases and the solvent solubility and non-crystallinity may not always be sufficient.

  The acid value of the carboxyl group-containing amideimide resin and carboxyl group-containing imide resin of the present invention is preferably 60 to 200 KOHmg / g, and particularly preferably 80 to 180 KOHmg / g. If it is 60-200 KOHmg / g, the performance which was excellent as hardened | cured material property will be demonstrated.

  When the aliphatic isocyanate compound having two or more isocyanate groups in the molecule and / or the alicyclic isocyanate compound (a) is composed of a composition comprising the isocyanurate type polyisocyanate (a2), it is further excellent. It is preferable because it exhibits cured properties and solubility performance. Specifically, the weight ratio between the diisocyanate monomer (a1) and the isocyanurate type polyisocyanate (a2) is excellent when W (a1) / W (a2) is 0 to 0.5, particularly 0 to 0.3. It is preferable because of its performance. When W (a1) / W (a2) = 0, it means that all isocyanate components are isocyanurate type polyisocyanate (a2), and the tetracarboxylic anhydride (b2) and tricarboxylic anhydride (b1 ) In the range of 0 to 1 ((b2) / (b1)).

In the imidization reaction, one or more kinds of isocyanate compound (a) and one or more kinds of tricarboxylic acid anhydride (b1) and / or tetracarboxylic acid anhydride (b2) are mixed in a solvent or in the absence of a solvent. The temperature is preferably increased while stirring. The reaction temperature is preferably 50 ° C to 250 ° C, particularly preferably 70 ° C to 180 ° C. When the reaction temperature is low, the reaction rate tends to be slow, and when the reaction temperature is high, side reactions and decomposition tend to occur. While the reaction is accompanied by decarboxylation, the hydroxyl-free and isocyanate groups form imide groups. The progress of the reaction can be followed by an analytical means such as an infrared vector, acid value, or isocyanate group quantification. The infrared spectrum, 2270 cm ^-1 which is the characteristic absorption of an isocyanate group was reduced as the reaction further acid anhydride group is reduced with a characteristic absorption at 1860 cm ^-1 and 850 cm ^-1. On the other hand, the absorption of imide groups increases at 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . The reaction may be terminated by lowering the temperature while confirming the target acid value, viscosity, molecular weight and the like. However, it is more preferable to continue the reaction until the isocyanate group disappears from the standpoint of stability over time. In addition, during the reaction or after the reaction, a catalyst, an antioxidant, a surfactant, other solvents, and the like may be added as long as the physical properties of the synthesized resin are not impaired.

  Examples of the carboxyl group-containing amideimide resin and carboxyl group-containing imide resin obtained by the method of the present invention include the following.

(Example 1) Imide resin represented by (Formula 1) obtained by reaction of aliphatic and alicyclic diisocyanates and aromatic tricarboxylic acid anhydride (b1).

(Ra represents a residue of a divalent aliphatic or alicyclic diisocyanate. N is a repeating unit of 0 to 30. Rb is represented by the following structural formula (Formula 2) or (Formula 3). ).

(R ₂ is an aromatic tricarboxylic acid residue that may have a substituent having 6 to 20 carbon atoms.) Rc is a structural unit represented by the following structural formula (formula 4).

(R ₂ is the same as above.))

(Example 2) An imide resin represented by (Formula 5) when the aromatic tricarboxylic acid anhydride (b1) and the tetracarboxylic acid anhydride (b2) are used in combination in Example 1.

(Rb ′ is a structural unit represented by the above (formula 2), (formula 3), or the following (formula 6),

(R ₃ represents an aromatic tetracarboxylic anhydride residue that may have a substituent having 6 to 20 carbon atoms.) Rc ′ is the above (Formula 4) or the following (Formula 7). , (Structural unit 8)

(R ₃ is the same as above.) Ra and n are the same as above. )

(Example 3) An imide resin represented by (formula 9) obtained by reaction of an aliphatic or alicyclic isocyanurate type triisocyanate and an aromatic tricarboxylic acid anhydride (b1).

(Rd is a trivalent organic group represented by the following (formula 10),

(Ra is the same as above.) Rb, Rc, and n are the same as above. )

(Example 4) It is represented by (Formula 11) obtained by reaction of an aliphatic or alicyclic isocyanurate type triisocyanate with an aromatic tricarboxylic acid anhydride (b1) and a tetracarboxylic acid anhydride (b2). Imide resin.

(Rb ', Rc' and Rd are the same as described above.)

Further, when a diisocyanate compound and an isocyanurate type triisocyanate are used in combination, the compound has a composite structure of the above (formula 1) and (formula 9), and the terminal structure thereof is Rc- in (formula 1). The structure of (Rc) _2- Rd- in Ra- and (Formula 9) is present at the molecular end. In addition, the structure of the main chain skeleton includes a unit of -Ra-Rb- in (Formula 1) and a structure of -Rd (Rc) -Rb- in (Formula 9). Furthermore, it is possible to use an aromatic isocyanate compound in combination so as not to impair the non-crystallinity and solubility. In that case, Ra in the above formula partially becomes a divalent aromatic group.

  The curable amide imide resin composition and curable imide resin composition of the present invention include the carboxyl group-containing amide imide resin and / or carboxyl group-containing imide resin (component (A)) and two or more epoxy groups in the molecule. It has an epoxy compound (component (B)). As the component (B), a known and commonly used epoxy resin can be used. Further, the component (B) preferably has a softening point of 50 ° C. or higher. If a softening point is 50 degreeC or more, the physical property of a curable amide imide resin composition and a curable imide resin composition will become more excellent.

  Examples of such epoxy resins include bisphenol A type epoxy, bisphenol S type epoxy, bisphenol F type epoxy, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and various diacids obtained by reacting dicyclopentadiene with various phenols. Epoxidized cyclopentadiene-modified phenolic resin, epoxidized 2,2 ′, 6,6′-tetramethylbiphenol, epoxidized 4,4′-methylenebis (2,6-dimethylphenol), naphthol, binaphthol, naphthol, Examples thereof include epoxy derived from a naphthalene skeleton such as a novolak modification of binaphthol, and an aromatic epoxy resin such as an epoxy resin obtained by epoxidizing a phenol resin having a fluorene skeleton. In addition, aliphatic epoxy resins such as neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4- Epoxy bicyclohexyl) An alicyclic epoxy resin obtained by oxidizing cyclohexene such as adipate, and a heterocyclic ring-containing epoxy resin such as triglycidyl isocyanurate can also be used.

  In addition, an epoxy group-containing polymerization resin obtained by polymerizing an unsaturated group of an epoxy compound having a polymerizable unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and other monomers having a polymerizable unsaturated bond Copolymers with can also be used.

  Examples of the compound having both (meth) acryloyl group and epoxy group include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxydibutyl (meth) acrylate glycidyl ether. , 6-hydroxyhexyl (meth) acrylate glycidyl ether, 5-hydroxy-3-methylpentyl (meth) acrylate glycidyl ether, (meth) acrylic acid-3,4-epoxycyclohexyl, lactone modified (meth) acrylic acid-3, 4-epoxycyclohexyl, vinylcyclohexene oxide and the like can be mentioned.

  The above-mentioned components (A) and (B) can be freely blended according to various desired physical properties, but in terms of thermal properties such as TG, water resistance, mechanical properties, etc. ( The number of moles n (COOH) of the carboxyl group of component A) and the number of moles n (EPOXY) of the epoxy group of component (B) are blended in the range of 4> n (EPOXY) / n (COOH)> 0.8. It is preferable. When n (EPOXY) / n (COOH) is 4 or more, TG is difficult to obtain as the characteristics of the cured coating film, and when it is 0.8 or less, there may be a problem with water resistance.

  When heat-curing, an epoxy-carboxylic acid-based curing catalyst or the like may be used in combination. Such epoxy-carboxylic acid curing catalysts include primary to tertiary amines for promoting the reaction, quaternary ammonium salts, nitrogen compounds such as dicyandiamide and imidazole compounds, TPP (triphenylphosphine). ), Known epoxy curing accelerators such as phosphine compounds such as alkyl-substituted trialkyl phonylphosphine and derivatives thereof, phosphophonium salts thereof, dialkylureas, carboxylic acids, phenols, or methylol group-containing compounds. Etc., and a small amount of these can be used in combination.

  In addition, the curable amide imide resin composition and / or curable imide resin composition comprising the component (A) and the component (B) are cured by heating after being applied to the object to be coated and cast. Can do. The curing temperature is preferably 80 ° C to 300 ° C, particularly 120 ° C to 250 ° C. Further, step curing at various temperatures may be performed. Further, a sheet-like or film-like composition semi-cured at a temperature of about 50 ° C. to 120 ° C. may be stored and treated at the above-described curing temperature when necessary. The curing reaction between the component (A) and the component (B) is basically a reaction between a carboxyl group and an epoxy group, and the type and blending ratio of the component (A) and the component (B), curing conditions, etc. are selected. By doing, the curable amide imide resin composition and / or curable imide resin composition which have the outstanding physical property etc. can be obtained. In the curable amide imide resin composition and curable imide resin composition of the present invention, if necessary, other solvents, various leveling agents, antifoaming agents, antioxidants, anti-aging agents, ultraviolet absorbers, anti-settling agents. , Various additives such as rheology control agents, known and commonly used fillers such as barium sulfate, silicon oxide, talc, clay, calcium carbonate, silica, colloidal silica, glass, various metal powders, glass fibers, carbon fibers, Kevlar fibers In addition, a fibrous filler such as phthalocyanine blue, phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, and known pigments such as silica, silica, and other adhesion imparting agents may be blended. Moreover, it is also possible to mix | blend polymers, such as an acrylic resin, a cellulose resin, a polyvinyl resin, polyphenylene ether, and polyether sulfone, as needed.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.

(Synthesis example 1) EDGA (diethylene glycol monomethyl ether acetate) 1496 parts, IPDI (isophorone diisocyanate) 888 parts (4 mol) and trimellitic anhydride 960 parts (5 mol) were added to a flask equipped with a stirrer, a thermometer and a condenser. The temperature was raised to 160 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a light brown clear liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely to 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . Absorption of imide groups was confirmed. The acid value was 85 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 1600 in terms of polystyrene. This resin is designated as X1.

(Synthesis Example 2) PGMAC (propylene glycol monomethyl ether acetate) 1464 parts, IPDI (isophorone diisocyanate) 888 parts (2 mol), NBDI (norbornane diisocyanate) 412 parts (2 mol) and a flask equipped with a stirrer, a thermometer and a condenser 960 parts (5 mol) of trimellitic anhydride was added, and the temperature was raised to 130 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 4 hours. The inside of the system became a light brown clear liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely to 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . Absorption of imide groups was confirmed. The acid value was 90 KOHmg / g in terms of solid content, and the molecular weight was 1,500 in number conversion molecular weight in terms of polystyrene. This resin is designated X2.

(Synthesis Example 3) 1496 parts EDGA (diethylene glycol monomethyl ether acetate), IPDI3N (isoisocyanurate type triisocyanate of isophorone diisocyanate: NCO% = 18.2) 2760 parts (4 mol) in a flask equipped with a stirrer, thermometer and condenser And 1728 parts (9 mol) of trimellitic anhydride were added, and the temperature was raised to 150 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a light brown clear liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely to 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . Absorption of imide groups was confirmed. The acid value was 95 KOHmg / g in terms of solid content, and the molecular weight was 4100 in terms of polystyrene. This resin is designated as X3.

(Synthesis Example 4) 4416 parts of EDGA (diethylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate of isophorone diisocyanate: NCO% = 18.2) 2760 parts (3 mol) in a flask equipped with a stirrer, a thermometer and a condenser 192 parts (1 mol) of H6XDI (hydrogenated xylene diisocyanate), 1728 parts (8 mol) of trimellitic anhydride and 218 parts (lmol) of pyromellitic anhydride were added, and the temperature was raised to 150 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system became a light brown clear liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely to 725 cm ⁻¹ , 1780 cm ⁻¹ and 1720 cm ⁻¹ . Absorption of imide groups was confirmed. The acid value was 105 KOHmg / g in terms of solid content, and the molecular weight was 5900 in terms of polystyrene. This resin is designated as X4.

(Synthesis Example 5) 4254 parts of EDGA (diethylene glycol monomethyl ether acetate) and IPDI3N (isoisocyanurate type triisocyanate of isophorone diisocyanate: NC 0% = 18.2) 2070 parts (3 mol) in a flask equipped with a stirrer, a thermometer and a condenser MDI (diphenylmethane diisocyanate) 250 parts (1 mol) and trimellitic anhydride 1728 parts (8 mol) were added, and the temperature was raised to 150 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and imides were obtained at 725 cm ⁻¹ , 1780 cm ⁻¹ , and 1720 cm ⁻¹ . Absorption of groups was confirmed. The acid value was 85 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 4100 in terms of polystyrene. This resin is designated as X5.

(Synthesis Example 6) 3786 parts of EDGA (diethylene glycol monomethyl ether acetate) and IPDI3N (isoisocyanurate type triisocyanate of isophorone diisocyanate: NC 0% = 18.2) 2076 parts (3 mol) in a flask equipped with a stirrer, a thermometer and a condenser HDI3N (hexamethylene diisocyanate: NC 0% = 24.7) 510 parts (lmol) and 1728 parts (9 mol) of trimellitic anhydride were added, and the temperature was raised to 150 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. As a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, disappeared completely, and imides were obtained at 725 cm ⁻¹ , 1780 cm ⁻¹ , and 1720 cm ⁻¹ . Absorption of groups was confirmed. The acid value was 120 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 5100 in terms of polystyrene. This resin is designated as X6.

(Synthesis example 7) 2384 parts of EDGA (diethylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate of isophorone diisocyanate: NCO% = 18.2) 1398 parts (2 mol) in a flask equipped with a stirrer, a thermometer and a condenser , 768 parts (4 mol) of trimellitic anhydride and 218 parts (lmo1) of pyromellitic anhydride were added, and the temperature was raised to 120 ° C. The reaction proceeded with foaming. The reaction was allowed to proceed for 8 hours at this temperature. The inside of the system becomes an orange clear liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappears and becomes 725 cm ⁻¹ , 1780 cm ⁻¹ , and 1720 cm ⁻¹ . Absorption of imide groups was confirmed. The acid value was 140 KOHmg / g in terms of solid content, and the molecular weight was a number average molecular weight of 2800 in terms of polystyrene. This resin is designated X7.

(Synthesis Example 8) 2488 parts EDGA (diethylene glycol monomethyl ether acetate), IPDI3N (isocyanurate type triisocyanate of isophorone diisocyanate: NCO% = 18.2) 1398 parts (2mo1) in a flask equipped with a stirrer, a thermometer and a condenser , 768 parts (4 mol) of trimellitic anhydride and 322 parts (lmol) of benzophenonetetracarboxylic dianhydride (BPDA) were added, and the temperature was raised to 120 ° C. The reaction proceeded with foaming. The reaction was carried out at this temperature for 8 hours. The inside of the system becomes an orange clear liquid, and as a result of measuring the characteristic absorption in the infrared spectrum, 2270 cm ^−1, which is the characteristic absorption of the isocyanate group, completely disappears and becomes 725 cm ⁻¹ , 1780 cm ⁻¹ , and 1720 cm ⁻¹ . Absorption of imide groups was confirmed. The acid value was 140 KOH mg / g in terms of solid content, and the molecular weight was 2900 in terms of polystyrene. This resin is designated as X8.

<Comparative Synthesis Example 1) In a flask equipped with a stirrer, a thermometer, and a condenser, 2210 parts of EDGA (diethylene glycol monomethyl anytel acetate), 1250 parts (4 mol) of MDI (diphenylmethane diisocyanate) and 960 parts of TMA (trimellitic anhydride) (5 mol) was added and the temperature was raised to 150 ° C. Although the reaction proceeded with foaming, a large amount of undissolved components were generated on the flask wall after about 1 hour, and after about 2 hours, all the contents were solidified and stirring was impossible. This resin taken out by pulverizing the contents is designated as Y-1.

(Comparative synthesis example 2) 1742 parts of EDGA (diethylene glycol monomethyl ether acetate), 870 parts (5 mol) of TDI (tolylene diisocyanate), and 872 parts of PMDA (hydromellitic anhydride) in a flask equipped with a stirrer, a thermometer and a condenser ( 4 mol) was added and the temperature was raised to 150 ° C. Although the reaction proceeded with foaming, a large amount of undissolved components were generated on the flask wall after about 1 hour, and after about 2 hours, all the contents were solidified and stirring was impossible. This resin obtained by pulverizing the contents is referred to as Y-2.

  The appearance of each resin after synthesis was evaluated as “◯” when it was a transparent liquid and “X” when it was solidified. Furthermore, each resin sample was coated on a glass substrate, and the appearance was evaluated as “◯” when uniformly coated, and “×” when coating defects such as repellency and crater were generated. Table 1 shows the composition, characteristic values, evaluation results, and the like of the resins shown in the above synthesis examples and comparative synthesis examples.

a1: Number of moles of diisocyanate monomer (mol)
a2: Number of moles of isocyanurate type polyisocyanate (mol)
a3: Number of moles of aromatic isocyanate (mol)
N: Number of moles of all isocyanate groups in the system (mol)
b1: Number of moles of tricarboxylic acid anhydride (mol)
b2: Number of moles of tetracarboxylic anhydride (mol)
M1: Number of moles of carboxyl group (mol)
M2: number of moles of acid anhydride group (mol)
M1 + M2: mol number of carboxyl group + mol number of acid anhydride group (mol)
(M1 + M2) / N: (number of moles of carboxyl group + number of moles of acid anhydride group (mol)) / number of moles of all isocyanate groups in the system (mol)
W (a1 / a2): Number of moles of diisocyanate monomer and isocyanurate type polyisocyanate (mol)
W {a3 / (a1 + a2 + a3)}:% by weight of aromatic isocyanate used in the isocyanate raw material used
b2 / b1: tetracarboxylic anhydride (mol) / tricarboxylic anhydride (mol)
IPDI: Isophorone diisocyanate NBDI: Norbornylene diisocyanate HXDI: Hydrogenated xylene diisocyanate IPDI3N: Isocyanurate trimer of isophorone diisocyanate HDI3N: Isocyanurate trimer of hexamethylene diisocyanate MDI: Diphenylmethane diisocyanate TDI: Tolylene diisocyanate TMA: Trimerit Acid anhydride PMDA: pyromellitic dianhydride BPDA: benzophenone tetracarboxylic dianhydride AN: acid value (KOHmg / g)
MN: Number average molecular weight (polystyrene conversion)
EDGA: Diethylene glycol monomethyl ether acetate PGMAC: Propylene glycol monomethyl ether acetate DMF: Dimethylformamide

Examples 1 to 8 and Comparative Examples 1 and 2
Using the resins obtained in the above synthesis examples and comparative synthesis examples, the curable amide imide resin composition and the curable imide resin composition were prepared with the formulation shown in Table 2.

Compounding amount of imide resin: Solid weight N680: Orthocresol novolac type epoxy resin Softening point 80 ° C. Epoxy equivalent = 212 g / eq
TPP: Triphenylphosphine (curing catalyst)
HP7200: Dicyclopentadiene-modified epoxy resin Softening point 62 ° C. Epoxy equivalent = 264 g / eq (Dainippon Ink Co., Ltd.)
EXA4700: naphthalene novolac type epoxy resin, softening point 93 ° C., epoxy equivalent = 163 g / eq (manufactured by Dainippon Ink Co., Ltd.)
N770: Phenol novolac type epoxy resin Softening point 70 ° C. Epoxy equivalent = 187 g / eq (Dainippon Ink Co., Ltd.)
EP850: Bisphenol A type epoxy resin Epoxy equivalent = 188 g / eq
TD2090: phenol novolac type epoxy resin, softening point 120 ° C., hydroxyl group equivalent = 105 g / eq
The compounding in Table 2 is a weight conversion value and indicates the compounding amount of the solid content. In the actual blending, dilution was performed with EDGA to a viscosity capable of being applied.

Test example 1 (appearance evaluation)
The curable amide imide resin composition and the curable imide resin composition obtained in the above Examples and Comparative Examples were coated on a glass substrate so that the film thickness after curing was 70 to 80 microns. Next, this coated plate was dried with a 120 ° C. dryer for 20 minutes and then cured at 150 ° C. for 1 hour to determine the appearance of the cured coating film. The results are shown in Table 3.
Evaluation criteria
A: Uniform and no foreign matter is seen.
X: A repellency, a foreign material, and an insoluble matter can be confirmed.

Test example 2 (TG, tensile test)
Preparation of test pieces for TG and tensile test The curable amide imide resin compositions and curable imide resin compositions obtained in the above examples and comparative examples were tin-coated so that the film thickness after curing would be 70 to 80 microns. Coating was performed on the substrate. Next, this coated plate was dried with a 120 ° C. dryer for 20 minutes, and then a two-level cured coating film was prepared by curing at 150 ° C. and 170 ° C. for 1 hour. After cooling to room temperature, the cured film was cut into a predetermined size, isolated from the substrate, and used as a measurement sample. These were measured by the following method. The results are shown in Table 3.

TG measurement method Dynamic viscoelasticity was measured, and the maximum temperature of Tan δ of the obtained spectrum was defined as TG. The dynamic viscoelasticity was measured under the following conditions.
Measuring instrument: Leo Vibron RSA-II (manufactured by Rheometric)
Jig: Pull chuck interval: 20 mm
Measurement temperature: 25 ° C to 300 ° C
Measurement frequency: 1HZ
Temperature increase rate: 3 ° C / min

Tensile test measuring method Measuring equipment: Tensilon (manufactured by Toyo Baldwin)
Sample shape: 10mX70mm
Between chucks: 20 mm
Pulling speed: 10mm / min
Measurement atmosphere: 22 ° C., 45% RH

Test Example 3 (PCT (Pressure Cooker) Resistance Test, Solder Heat Resistance Test)
Preparation of sample pieces for PCT resistance test and solder heat resistance test On glass epoxy printed circuit board on which copper circuit patterns were formed by previously etching the curable amide imide resin compositions and curable imide resin compositions obtained in the above examples and comparative examples. Further, the coating was performed so that the film thickness after curing was 70 to 80 microns. Next, this coated plate was dried with a 120 ° C. dryer for 20 minutes and then cured at 170 ° C. for 1 hour to prepare a test piece. These were measured by the following method. The results are shown in Table 3.

PCT resistance test method PCT tester (Hirayama Manufacturing Co., Ltd. PC-304RllI) 121 ° C, 100% RH (under saturated vapor pressure) for 50 hours, after returning to room temperature, the appearance changes visually. Then, a cross-cut cello tape (registered trademark) peel test was performed for adhesion. The appearance was evaluated according to the following criteria.
A: No change is seen from that before the PCT test.
A: Almost no change is seen from before the PCT test.
(Triangle | delta): A blister etc. are seen in part.
X: Blister or whitening, dissolution, etc. occur on the entire surface.

Solder heat resistance test method A test piece prepared according to the test method of JlS C-6481 was subjected to 3 cycles, with 1 cycle flowing in a solder bath at 260 ° C. for 10 seconds. Abnormalities such as swelling of the coating film and adhesion were comprehensively evaluated according to the following criteria.
A: No change is seen at all.
○: Almost no change is observed.
(Triangle | delta): A defect, peeling, etc. are seen partially.
X: A coating film defect, peeling, etc. have occurred on the entire surface.

TG: Glass transition temperature (° C)
Breaking strength: MPa
Elongation at break:%

  As is apparent from the results in Table 3, all the examples were dissolved in a general-purpose solvent and had excellent appearance and workability after curing. As seen in Comparative Examples 1 and 2, those using aromatic isocyanate as the isocyanate component did not dissolve in the solvent, solidified, and were not compatible when blended with epoxy. The coating appearance was poor, and a sample for subsequent physical property evaluation could not be prepared. The cured coating films of the examples show very high TG, and particularly have a glass transition point higher than the curing temperature, and can be said to be materials that can exhibit heat resistance even at low temperatures. Also, it has very high resistance in PCT resistance and solder heat resistance tests. On the other hand, the composition of Comparative Examples 4 and 5 is an epoxy / phenolic curing system that obtains a general heat-resistant coating film, but has a lower TG compared to the Examples. Moreover, it was a bad result also in breaking elongation, PCT tolerance, and solder heat resistance. In Comparative Example 5, the cured coating film was brittle, and the sample for the tensile test could not be isolated.

Claims (3)

  An aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule, a tricarboxylic acid anhydride (b1) and / or a tetracarboxylic acid anhydride (b2) A method for producing a carboxyl group or acid anhydride group-containing amideimide resin or a carboxyl group or acid anhydride group-containing imide resin by reacting in a polar solvent containing no atoms and sulfur atoms, wherein the polar solvent is an ether type A resin, characterized in that the aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule contains an isocyanurate type polyisocyanate (a2). Production method.   The production method according to claim 1, wherein the acid value of the carboxyl group or acid anhydride group-containing amideimide resin or the carboxyl group or acid anhydride group-containing imide resin is 60 to 200 KOHmg / g.   The aliphatic isocyanate compound and / or alicyclic isocyanate compound (a) having two or more isocyanate groups in the molecule is composed of a diisocyanate monomer (a1) and an isocyanurate type polyisocyanate (a2), or isocyanate It is composed only of the nurate type polyisocyanate (a2), and the weight ratio ((a1) / (a2)) of the diisocyanate monomer (a1) and the isocyanurate type polyisocyanate (a2) is 0 to 0.5. The manufacturing method of Claim 1 or 2 characterized by these.